Jane C. Chuang

Phase distribution and artifact formation in ambient air sampling for polynuclear aromatic hydrocarbons

Abstract Laboratory and field sampling experiments were conducted to determine the phase-distribution of polynuclear aromatic hydrocarbons (PAH) in the ambient atmosphere and to determine the potential for artifact formation due to volatilization and ozone (O3) reaction during normal sampling conditions. The study was conducted in two segments to investigate both summer and winter ambient temperature effects. The winter measurements reflect stronger association of PAH with the particulate phase than the summer data, but data from both seasons show appreciable filter losses due to volatilization of phenanthrene, anthracene, fluoranthene, benz(a)anthracene and chrysene. No evidence was found for volatilization of the heavier PAH, including benzo(e)pyrene, benzo(a)pyrene, indeno(l,2,3-c,d)pyrene, benzo(g,h,i)perylene and coronene. Although O3 reacted readily with particulate matter that was freshly spiked with PAH in the laboratory experiments, no evidence was found for reaction of O3 with particulate matter during the field sampling experiments.

Polycyclic aromatic hydrocarbons and their derivatives in indoor and outdoor air in an eight-home study

Abstract A pilot field study was performed in Columbus, OH, during the winter of 1986/1987. The objectives were to determine the feasibility of the use of a newly developed quiet sampler in indoor air sampling for particles and semivolatile organic compounds (SVOC) and to measure the concentrations of polycyclic aromatic hydrocarbons (PAH), PAH derivatives, and nicotine in air in selected residences. Eight homes were chosen for sampling on the basis of these characteristics: electric/gas heating system, electric/gas cooking appliances, and the absence/presence of environmental tobacco smoke (ETS). The indoor sampler was equipped with a quartz-fiber filter to collect particles followed by XAD-4 resin to trap SVOC. A PS-1 sampler with a similar sampling module was used outdoors. The indoor air was sampled in the kitchen and living room areas over two consecutive 8-h periods. The outdoor air was sampled concurrently with the indoor samples over a 16-h period. Fifteen PAH, five nitro-PAH, five oxygenated PAH, and three nitrogen heterocyclic compounds were determined in these samples. The most abundant PAH found indoors was naphthalene. The indoor concentrations of PAH derivatives were lower than those of their parent compounds. Average concentrations of all but three target compounds (naphthalene dicarboxylic acid anhydride, pyrene dicarboxylic acid anhydride, and 2-nitrofluoranthene) were higher indoors than outdoors. Environmental tobacco smoke was the most significant influence on indoor pollutant levels. Homes with gas heating systems had higher indoor pollutant levels than homes with electric heating systems. However, the true effects of heating and cooking systems were not characterized as accurately as the effects of ETS because of the small sample sizes and the lack of statistical significance for most pollutant differences in the absence of ETS. The concentrations of PAH marker compounds (phenanthrene, fluoranthene, and pyrene) correlated well with the concentrations of other target compounds. Quinoline and isoquinoline can be used to indicate indoor levels of ETS.

Indoor air sampling and mutagenicity studies of emissions from unvented coal combustion.

To develop sampling strategies and bioassay protocols for indoor air containing emissions from coal combustion in homes of the rural Xuan Wei County in China, the authors developed a medium-volume sampler to collect the <10-..mu..m particles and semivolatile organics by a filter and an XAD-2 resin, respectively. A high-volume particulate sampler was used for comparison. The coal was burned under conditions that simulated the open-pit combustion that occurs in Xuan Wei. High-volume and medium-volume sampling yielded similar, high particulate concentrations 38-39 mg/m/sup 3/. Fifteen percent of the total extractable organic mass was collected in the XAD-2 resin, and the remaining 85% was retained in the filter. The polycyclic aromatic hydrocarbons found in the XAD were composed of four or fewer rings. In the Ames Salmonella assay, the XAD sample showed low mutagenic activity, and most of the mutagenic activity was found in the filter. The coal combustion emitted both direct- and indirect-acting mutagens, most of which were frameshift mutagens. 12 references, 2 figures, 3 tables.

Concentrations and phase distributions of nitrated and oxygenated polycyclic aromatic hydrocarbons in ambient air

Abstract The concentrations of nitrated and oxygenated polycyclic aromatic hydrocarbons (PAH) in ambient air, both in the vapor phase and adsorbed on airborne particles, were measured over a 12-month period in Houston, Texas. Seasonal variations in the levels of the target compounds were weakly related to changes in ambient temperature, but more strongly related to fluctuations in the levels of ozone (O3), nitrogen dioxide (NO2), and other oxides of nitrogen (NOx). Phase distributions of the target compounds were determined by the denuder difference method. These phase distributions varied greatly over 12 months and were related to the molecular sizes, hence vapor pressures, of the compounds, but few significant associations were found between the percentages of compounds present in the vapor phase and ambient temperatures.

Evaluation of analytical methods for determining pesticides in baby foods and adult duplicate-diet samples

Abstract Determination of pesticides in food is often complicated by the presence of fats and requires multiple clean-up steps before analysis. Cost-effective methods are needed for analyzing the large number of samples generated in large-scale exposure studies. We examined two extraction methods, supercritical fluid extraction (SFE) and accelerated solvent extraction (ASE), coupled with various clean-up techniques for the analysis of pesticides in baby foods and exposure samples. The SFE-gas chromatogram/mass spectrometry (GC/MS) method did not provide quantitative recoveries (

The mutagenicity of indoor air particles in a residential pilot field study: Application and evaluation of new methodologies

Abstract The mutagenicity of indoor air paniculate matter has been measured in a pilot field study of homes in Columbus, Ohio during the 1984 winter. The study was conducted in eight all natural-gas homes and two all electric homes. Paniculate matter and semi-volatile organic compounds were collected indoors using a medium volume sampler. A micro-forward mutation bioassay employing Salmonella typhimurium strain TM 677 was used to quantify the mutagenicity in solvent extracts of microgram quantities of indoor air particles. The mutagenicity was quantified in terms of both mutation frequency per mg of organic matter extracted and per cubic meter of air sampled. The combustion source variables explored in this study included woodburning in fireplaces and cigarette smoking. Homes in which cigarette smoking occurred had the highest concentrations of mutagenicity per cubic meter of air. The average indoor air mutagenicity per cubic meter was highly correlated with the number of cigarettes smoked. When the separate sampling periods in each room were compared, the mutagenicity in the kitchen samples was the most highly correlated with the number of cigarettes smoked.

Variability of hazardous air pollutants in an urban area

Abstract The variability of hazardous air pollutants (HAPs) is an important factor in determining human exposure to such chemicals, and in designing HAP measurement programs. This study has investigated the factors which contribute to HAP variability in an urban area. Six measurement sites separated by up to 12 km collected data with 3 h time resolution to examine spatial variability within neighborhoods and between neighborhoods. The measurements were made in Columbus, OH. The 3 h results also were used to study temporal variability, and duplicate samples collected at each site were used to determine the component of variability attributable to the measurement process. Hourly samples collected over 10 days at one site provided further insight into the temporal resolution needed to capture short-term peak concentrations. Measurements at the 6 spatial sites focused on 78 chemicals. Twenty-three of these species were found in at least 95% of the 3 h samples, and 39 chemicals were present at least 60% of the time. The relative standard deviations for most of these 39 frequently detected chemicals was 1.0 or lower. Variability was segmented into temporal, spatial, and measurement components. Temporal variation was the major contributor to HAP variability for 19 of the 39 frequently detected compounds, based on the 3 h data. Measurement imprecision contributed less than 25% for most of the volatile organic species, but 30% or more of the variability for carbonyl compounds, trace elements, and particle-bound extractable organic mass. Interestingly, the spatial component contributed less than 20% of the total variability for all the chemicals except sulfur. Based on the data with hourly resolution, peak to median ratios (hourly peak to 24 h median) averaged between 2 and 4 for most of the volatile organic compounds, but there were two species with peak to median ratios of about 10.

Chemical characterization of indoor air of homes from communes in Xuan Wei, China, with high lung cancer mortality rate

In a rural county, Xuan Wei, China, the lung cancer mortality rate is among Chinas highest, especially in women. This mortality rate is more associated with indoor air burning of smoky coal, as opposed to smokeless coal or wood, for cooking and heating under unvented conditions. Homes using different fuels from communes with high and low lung cancer mortality rates were sampled for particulate matter ( 70%), including PAH, followed by homes using wood and smokeless coal. The major components present in the smoky coal filter samples were PAH and alkylated PAH. The smokeless coal filter samples exhibited profiles which were similar to the smoky coal samples except that some sulfur compounds were found. The estimated concentration levels of PAH in the smokeless coal samples were about one to two orders of magnitude lower than those of the smoky coal samples. In addition to PAH, aliphatic compounds and fatty acids were the major components found in the wood samples. Selected sample extracts from homes using smoky coal were fractionated into four fractions, and the results showed that the PAH and polar fractions have high mutagenic activity. Chemical characterization of the PAH fraction indicated that concentrations of some alkylated PAH were higher than those of their parent compounds. Chemical characterization of the polar fractions showed that nitrogen heterocyclic compounds are present.

Development and evaluation of an enzyme-linked immunosorbent assay (ELISA) method for the measurement of 2,4-dichlorophenoxyacetic acid in human urine

An enzyme-linked immunosorbent assay (ELISA) method was developed to quantitatively measure 2,4-dichlorophenoxyacetic acid (2,4-D) in human urine. Samples were diluted (1:5) with phosphate-buffered saline containing 0.05% Tween and 0.02% sodium azide, with analysis by a 96-microwell plate immunoassay format. No clean up was required as dilution step minimized sample interferences. Fifty urine samples were received without identifiers from a subset of pesticide applicators and their spouses in an EPA pesticide exposure study (PES) and analyzed by the ELISA method and a conventional gas chromatography/mass spectrometry (GC/MS) procedure. For the GC/MS analysis, urine samples were extracted with acidic dichloromethane (DCM); methylated by diazomethane and fractionated by a Florisil solid phase extraction (SPE) column prior to GC/MS detection. The percent relative standard deviation (%R.S.D.) of the 96-microwell plate triplicate assays ranged from 1.2 to 22% for the urine samples. Day-to-day variation of the assay results was within +/-20%. Quantitative recoveries (>70%) of 2,4-D were obtained for the spiked urine samples by the ELISA method. Quantitative recoveries (>80%) of 2,4-D were also obtained for these samples by the GC/MS procedure. The overall method precision of these samples was within +/-20% for both the ELISA and GC/MS methods. The estimated quantification limit for 2,4-D in urine was 30ng/mL by ELISA and 0.2ng/mL by GC/MS. A higher quantification limit for the ELISA method is partly due to the requirement of a 1:5 dilution to remove the urine sample matrix effect. The GC/MS method can accommodate a 10:1 concentration factor (10mL of urine converted into 1mL organic solvent for analysis) but requires extraction, methylation and clean up on a solid phase column. The immunoassay and GC/MS data were highly correlated, with a correlation coefficient of 0.94 and a slope of 1.00. Favorable results between the two methods were achieved despite the vast differences in sample preparation. Results indicated that the ELISA method could be used as a high throughput, quantitative monitoring tool for human urine samples to identify individuals with exposure to 2,4-D above the typical background levels.

Comparison of immunoassay and gas chromatography–mass spectrometry for measurement of polycyclic aromatic hydrocarbons in contaminated soil

Polycyclic aromatic hydrocarbons (PAHs) are frequently encountered in the environment and may pose health concerns due to their carcinogenicity. A commercial enzyme-linked immunosorbent assay (ELISA), was evaluated as a screening method for monitoring PAHs at contaminated sites. The ELISA was a carcinogenic PAH (C-PAH) RaPID assay testing kit that cross-reacts with several PAHs and utilizes benzo[a]pyrene (BaP) as a calibrator. Soil samples were extracted with 50% acetone in dichloromethane (DCM) for analysis by ELISA and gas chromatography–mass spectrometry (GC–MS). The overall method precision was within ±30% for ELISA and within ±20% for GC–MS. Recovery data for spiked soils ranged from 46 to 140% for BaP as determined by ELISA. Recoveries data of the GC–MS surrogate standards, 2-fluorobiphenyl and chrysene, were greater than 70%. The GC–MS procedure detected a total of 19 priority PAHs (2–6-ring PAHs) including seven probable human carcinogens (4–6-ring B2-PAHs). The ELISA results were compared to GC–MS summation results for the total 19 target PAHs as well as for the subset of the seven B2-PAH compounds. For all soil samples, the PAH concentrations derived from ELISA were greater than the sum of B2-PAH concentrations obtained by GC–MS. ELISA determinations were also frequently greater than the results obtained by GC–MS for the total 19 PAH compounds. This discrepancy can be expected, since the ELISA is a screening assay for the detection of several related PAHs while the GC–MS procedure detects priority PAH compounds. Thus, only a subset of PAHs (e.g. 19 PAHs) in the soil samples were measured by GC–MS while additional PAHs, including alkylated PAHs, and PAH derivatives have been demonstrated to be cross-reactive in the C-PAH ELISA. Results of paired tests show that the PAH data from ELISA and GC–MS methods are significantly different (P<0.001), but highly correlated. The ELISA data had a strong positive relationship with the GC–MS summation data for the B2-PAHs as well as for the 19 PAHs targeted by the GC–MS method. Results indicate that the ELISA may be useful as a broad screen for monitoring PAHs in environmental samples.